EP1698631B1 - Ionische flüssigkeit, verfahren zu deren herstellung, doppelschichtiger kondensator, der diese enthält, und lithiumbatterie - Google Patents

Ionische flüssigkeit, verfahren zu deren herstellung, doppelschichtiger kondensator, der diese enthält, und lithiumbatterie Download PDF

Info

Publication number
EP1698631B1
EP1698631B1 EP04807680A EP04807680A EP1698631B1 EP 1698631 B1 EP1698631 B1 EP 1698631B1 EP 04807680 A EP04807680 A EP 04807680A EP 04807680 A EP04807680 A EP 04807680A EP 1698631 B1 EP1698631 B1 EP 1698631B1
Authority
EP
European Patent Office
Prior art keywords
ionic liquid
alkyl
same
och
nmr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP04807680A
Other languages
English (en)
French (fr)
Other versions
EP1698631A1 (de
EP1698631A4 (de
Inventor
H. Matsumoto
Z. Zhou
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute of Advanced Industrial Science and Technology AIST
Original Assignee
National Institute of Advanced Industrial Science and Technology AIST
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Institute of Advanced Industrial Science and Technology AIST filed Critical National Institute of Advanced Industrial Science and Technology AIST
Publication of EP1698631A1 publication Critical patent/EP1698631A1/de
Publication of EP1698631A4 publication Critical patent/EP1698631A4/de
Application granted granted Critical
Publication of EP1698631B1 publication Critical patent/EP1698631B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to ionic liquids, and more particularly to ionic liquids with low viscosities and melting points as well as high conductivities and electrochemical stabilities.
  • the present invention also relates to a method of producing ionic liquids as well as lithium batteries (for example, lithium-ion batteries, lithium primary batteries and lithium secondary batteries, and particularly lithium secondary batteries) and electric double-layer capacitors comprising the ionic liquids.
  • lithium batteries for example, lithium-ion batteries, lithium primary batteries and lithium secondary batteries, and particularly lithium secondary batteries
  • Ionic liquids have attracted special attention for the past several years, owing to their potential for application as the electrolytes, reaction media and catalysts for organic syntheses for a variety of electrochemical devices, such as lithium secondary batteries, solar cells, actuators, electric double-layer capacitors and the like.
  • electrochemical devices such as lithium secondary batteries, solar cells, actuators, electric double-layer capacitors and the like.
  • ionic liquids as such electrolytes have the main advantages of flame retardancy, non-volatility and high thermal stability.
  • ionic liquids containing these anions suffer from problems such as low conductivity at low temperature, in particular.
  • Patent Publication 3 discloses boron compounds; however, for example, triethylmethylammonium-CF 3 BF 3 manufactured in the Examples has a high melting point of 181°C, and therefore cannot serve as an ionic liquid.
  • Patent Publication 4 discloses the BF 3 CF 3 salt of 1-ethyl-3-methylimidazolium in Example 1.
  • An object of the present invention is to provide ionic liquids with low viscosities, low melting points and high conductivities by improving the anionic and cationic components.
  • the present invention also relates to electric double-layer capacitors and lithium batteries comprising such ionic liquids, especially to lithium secondary batteries.
  • an ionic liquid with a low viscosity and low melting point as well as high conductivity at low temperatures can be obtained using at least one anion represented by [BF 3 (C n F 2n+1 )] - where n represents 1, 2, 3 or 4, or using such an anion together with a salt containing a particular aliphatic or heterocyclic ammonium-based cation.
  • the present invention provides ionic liquids and a production method therefor as well as electric double-layer capacitors and lithium batteries using such ionic liquids, as itemized below:
  • the present invention provides ionic liquids with low viscosities and melting points.
  • Ionic liquids of the present invention are especially suitable for use in lithium batteries and electric double-layer capacitors.
  • the ionic liquids are also useful in solar cells, electrochemical sensor devices, electrochemical (electrochromic) display devices, and the like.
  • Ionic liquids for use in the present invention typically have melting points of 150°C or less, preferably 80°C or less, more preferably 60 °C or less, still more preferably 40 °C or less, and even more preferably 25°C or less.
  • ionic liquids with melting points of 150°C or less can be widely used in fuel cells.
  • Ionic liquids for use in energy devices such as solar cells, lithium batteries, capacitors, etc., and electrochemical devices such as electrochromic devices, electrochemical sensors, etc. preferably have melting points of room temperature (25°C) or less, and more preferably 0 °C or less.
  • the anionic component of the ionic liquid for use in the present invention is at least one member selected from the group consisting of BF 3 (CF 3 ) - , [BF 3 (C 2 F 5 )] - , [BF 3 (C 3 F 7 )] - (i.e., [BF 3 (n-C 3 F 7 )] - and [BF 3 (i-C 3 F 7 )] - ), and [BF 3 (C 4 F 9 )] - (i.e., [BF 3 (n-C 4 F 9 )] - , [BF 3 (i-C 4 F 9 )] - , [BF 3 (sec-C 4 F 9 )] - , and [BF 3 (tert-C 4 F 9 )] - ); and preferably at least one member selected from the group consisting of [BF 3 (CF 3 )] - , [BF 3 (C 2 F 5 )] - , and [BF 3 (C 3 F 7 )] - (
  • the above-mentioned anions are known compounds, and are described in, for example, G. A. Molander, B. J. Hoag, Organometallics, 22, (2003), 3313 ; and Zhi-Bin Zhou, Masayuki Takeda, Makoto Ue, J. Fluorine. Chem., 123 (2003) 127 .
  • the ionic liquid of the present invention may comprise a single anionic component, or two or more anionic components to further decrease the melting point.
  • a cationic component such as an alkali metal ion (Na + , K + , Li + , Cs + , etc.), an alkaline-earth metal
  • an ionic liquid consisting of [BF 3 (C n F 2n+1 )] - wherein n represents 1, 2, 3, or 4 and an organic ammonium ion can be preferably obtained by mixing an (organic ammonium) + (OH) - salt with a [BF 3 (C n F (2n+1 )] - H + salt, wherein n represents 1, 2, 3, or 4, which is prepared by passing through an ion exchange resin; and removing water.
  • a salt exchange reaction for obtaining an ionic liquid can be carried out by solvent extraction when the desired molten salt is capable of being extracted.
  • the anion(s) of the ionic liquid used is at least one member selected from the group consisting of anions represented by [BF 3 (C n F 2n+1) ] - wherein n represents 1, 2, 3, or 4, such an anion being the primary component; however, other anions may also be added so long as the resulting salt is an ionic liquid.
  • organic ammonium compounds include salts of organic ammonium cations with hydroxide (OH - ), halogen, nitrate, sulfate, phosphate, perchlorate, methanesulfonate, toluenesulfonate ions, and the like.
  • the ionic liquid may also be produced using at least one anion selected from the group represented by [BF 3 (C n F 2n+1 )] - wherein n represents 1, 2, 3 or 4 in the form of, e.g., silver, calcium, barium and/or the like salts, together with an organic ammonium ion, in the form of, e.g., a halide salt, sulfate salt or the like, to form a sparingly soluble salt, such as a silver halide, barium sulfate, calcium sulfate or the like resulting from aforementioned counterions, and removing the formed salt.
  • a sparingly soluble salt such as a silver halide, barium sulfate, calcium sulfate or the like resulting from aforementioned counterions, and removing the formed salt.
  • the ionic liquid may be prepared by mixing (organic ammonium(s) of general formula (I)) + (OH) - with at least one member selected from the group consisting of anions represented by [BF 3 (C n F 2n+1 )] - H + wherein n represents 1, 2, 3, or 4.
  • alkyl groups include C 1-20 , preferably C 1-10, more preferably C 1-6 , and still more preferably C 1-3 linear or branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and the like.
  • alkyl groups include C 1-20 , preferably C 1-10, more preferably C 1-6 , and still more preferably C 1-3 linear or branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
  • fluoroalkyl groups include C 1-10 , preferably C 1-10 , more preferably C 1-6 , and still more preferably C 1-3 polyfluoroalkyl and perfluoroalkyl groups wherein at least one of the hydrogen atoms of an above-mentioned alkyl group is substituted with fluorine.
  • alkoxy groups include C 1-20 , preferably C 1-10 , more preferably C 1-6 , and still more preferably C 1-3 linear or branched alkoxy groups, wherein an aforementioned alkyl group is attached to oxygen.
  • alkoxy and alkyl groups of alkoxyalkyl groups are the same as mentioned above.
  • alkoxyalkyl groups include C 1-20 , preferably C 1-10 , more preferably C 1-6 , and still more preferably C 1-3 linear or branched alkyl groups substituted with C 1-20 , preferably C 1-10 , more preferably C 1-6 , and still more preferably C 1-3 linear or branched alkoxy groups; such as, preferably -(C 1-3 alkylene)-O-(C 1-3 alkyl); and more preferably methoxymethyl (CH 2 OCH 3 ), methoxyethyl (CH 2 CH 2 OCH 3 ), ethoxymethyl (CH 2 OCH 2 CH 3 ), ethoxyethyl (CH 2 CH 2 OCH 2 CH 3 ), methoxypropyl (CH 2 CH 2 CH 2 OCH 3 ), ethoxypropyl (CH 2 CH 2 CH 2 OCH 2 CH 3 ), propoxymethyl (CH 2 OCH 2 CH
  • polyether groups include those represented by -(CH2) n1 -O-(CH 2 CH 2 O) n2 -(C 1-4 alkyl); -(CH 2 ) n1 -O-(CH 2 CH(CH 3 )O) n2 -(C 1-4 alkyl); or -(CH 2 ) n1 -O-(CH(CH 3 )CH 2 O) n2 -(C 1-4 alkyl), where n1 is an integer from 1 to 4; n2 is an integer from 1 to 4; and the C 1-4 alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or the like.
  • Alkenyl groups or the aforementioned alkyl groups may have one or more of -O-,-COO- and -CO- interposed between C-C single bonds at any positions to form ether, ester, or ketone structures.
  • alkyl groups with 3 or more carbon atoms attached to a pyrrolidine, piperidine, or morpholine ring include C 3-20 , preferably C 3-10 , and more preferably C 3-7 linear or branched alkyl groups, such as n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and the like.
  • C 3-10 alkyl groups represented by R 4 are C 3-10 , preferably C 4-8 , and more preferably C 4-6 linear or branched alkyl groups, such as n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and the like.
  • C 3-10 alkyl groups represented by R 4 are C 3-10 , preferably C 4-8 , and more preferably C 4-6 linear or branched alkyl groups, such as n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pen
  • R 1 and R 2 taken together with the nitrogen atom to which they are attached may form pyrrolidinium, piperidinium or morpholinium.
  • Examples of preferable ammonium ions include methyldiethyl(n-, i-, sec-, or tert-)butylammonium (N 1224 ), dimethylethyl(n-, i-, sec-, or tert-)butylammonium (N 1124 ), trimethyl(n-, i-, sec-, or tert-)butylammonium (N 1114 ), triethyl(n-, i-, sec-, or tert-)butylammonium (N 2224 ), methyldiethylhexylammonium (N 1226 ), dimethylethylhexylammonium (N 1126 ), trimethylhexylammonium (N 1116 ), and triethylhe
  • R 1 R 2 R 3 R 4 same or different, each being methyl or ethyl C 3-10 alkyl alkyl alkyl alkoxyalkyl alkyl alkyl alkyl polyether Pyrrolidine ring alkyl alkoxyalkyl Pyrrolidine ring alkyl C 3 or more alkyl Pyrrolidine ring alkyl polyether Pyrrolidine ring alkyl alkoxyalkyl Pyrrolidine ring alkyl C 3 or more alkyl Pyrrolidine ring alkyl polyether Pyrrolidine ring alkyl alkoxyalkyl Pyrrolidine ring alkyl C 3 or more alkyl Pyrrolidine ring alkyl polyether morpholine ring alkyl alkoxyalkyl morpholine ring alkyl C 3 or more alkyl morpholine ring alkyl polyether
  • Ionic liquids of the present invention are capable of easily dissolving electrolytes such as lithium salts, and are also incombustible and have low viscosities. Therefore, the ionic liquids can be suitably used as electrolyte solvents for lithium batteries such as lithium secondary batteries, electric double-layer capacitors, solar cells, electrochemical sensor devices, electrochemical (electrochromic) display devices and the like.
  • lithium batteries such as lithium secondary batteries, electric double-layer capacitors, solar cells, electrochemical sensor devices, electrochemical (electrochromic) display devices and the like.
  • K[CF 3 BF 3 ] was prepared in the manner as described in G. A. Molander, B. J. Hoag, Organometallics, 22, (2003), 3313 , and then the K[CF 3 BF 3 ] was subjected to a cation exchange process as described in S. Mori, K. Ida, and M. Ue, US Pat. 4, 892, 944 (1990 ), thereby yielding aqueous H solv .[CF 3 BF 3 ]solv.
  • K[C 2 F 5 BF 3 ], K[n-C 3 F 7 BF 3 ] and K[n-C 4 F 9 BF 3 ] were prepared in the manner as described in Zhi-Bin Zhou, Masayuki Takeda, Makoto Ue, J. Fluorine. Chem, 123 (2003) 127 , and then the K[C 2 F 5 BF 3 ], K[n-C 3 F 7 BF 3 ] and K[n-C 4 F 9 BF 3 ] were each subjected to a cation exchange process as described in S. Mori, K. Ida, and M. Ue, US Pat. 4, 892, 944.
  • the halide thus obtained was converted to the hydroxide (N 102122 + (OH - ) with an anion exchange resin.
  • each quaternary ammonium salt product was recrystallized in acetone, and the formation of trimethylmethoxyethylammonium bromide (N 102111 + Br - ), dimethylethylmethoxyethylammonium bromide (N 102112 + Br - ) and triethylmethoxyethylammonium bromide (N 102222 + Br - ) was confirmed by NMR.
  • the bromides thus obtained were converted to the hydroxides (N 102111 + OH - , N 102112 + OH - and N 102222 + OH - , respectively) with an anion exchange resin.
  • C5 (Pi 102.1 + Br - ), C6 (Py 102.1 + Br - ) and C11 (Mor 1.102 + Br - ) were synthesized in a similar manner as in synthesis (2) above, except for using N-methylpyrrolidine, N-methylpiperidine and N-methylmorpholine instead of the amines (triethylamine, dimethylethyl amine and triethylamine).
  • C7 N 102.112 + Br -
  • C8 N 1224 + Br -
  • C9 Py 101.1 + Br -
  • C10 Mor 14 + Br -
  • synthesis (2) was synthesized in a similar manner as in synthesis (2) above, except for using dimethylethylamine, methyldiethylamine, methylpyrrolidine or N-methylmorpholine as the amine; and using CH 3 CH 2 CH 2 CH 2 Br or CH 3 OCH 2 Br as the bromide.
  • methyltriethylammonium hydroxide (N 1222 ⁇ OH - ) and tetraethylammonium hydroxide (N 2222 ⁇ OH - ) were prepared by a known process.
  • the ionic liquid was concentrated to about 20 ml under reduced pressure at 30 to 40 °C, and then the bottom layer was separated, followed by washing with deionized water (10 ml) and toluene (20 ml ⁇ 2). The resulting ionic liquid bottom layer was dried under vacuum (0.03 mmHg) at 60 °C for 12 hours, so as to yield the target ionic liquid.
  • Tables 3 to 5 below show the combinations of the anions and cations along with their physical values.
  • Fig. 1 shows a linear sweep voltammogram of the [C 2 F 5 BF 3 ] salt.
  • Fig. 2 shows the results of linear sweep voltammetry performed on N 102112 [CF 3 BF 3 ] and EMI [CF 3 BF 3 ] at room temperature in a glove box (O 2 and water ⁇ 5 ppm) filled with argon for the evaluation of electrochemical stability (working electrode: glassy carbon; counter electrode: platinum; reference electrode: a platinum wire immersed in iodine redox-containing EMI-TFSI. Calculated using the redox potential of ferrocene in the ionic liquid as an internal standard. Measured by ALS, model 660 electrochemical analyzer).

Claims (4)

  1. Ionische Flüssigkeit umfassend mindestens einen Bestandteil ausgewählt aus der Gruppe bestehend aus
    Figure imgb0037
    Figure imgb0038
    Figure imgb0039
    Figure imgb0040
    Figure imgb0041
    Figure imgb0042
    Figure imgb0043
    Figure imgb0044
    Figure imgb0045
    Figure imgb0046
    Figure imgb0047
    Figure imgb0048
    Figure imgb0049
    Figure imgb0050
    Figure imgb0051
    Figure imgb0052
    Figure imgb0053
    Figure imgb0054
    Figure imgb0055
    Figure imgb0056
    Figure imgb0057
    Figure imgb0058
  2. Elektrischer doppelschichtiger Kondensator umfassend die ionische Flüssigkeit nach Anspruch 1.
  3. Lithiumbatterie umfassend die ionische Flüssigkeit nach Anspruch 1.
  4. Verfahren zum Herstellen einer ionischen Flüssigkeit nach Anspruch 1, umfassend das Mischen einer Verbindung enthaltend als anionische Komponente mindestens ein Anion dargestellt durch [BF3(CnF2n+))]-, wobei n 1, 2, 3 oder 4 darstellt, mit einer Verbindung, die als kationische Komponente mindestens ein organisches Ammoniumion enthält, die gleich oder verschieden sind, wobei jedes aus der Gruppe ausgewählt ist bestehend aus
    Figure imgb0059
    Figure imgb0060
    Figure imgb0061
    Figure imgb0062
    Figure imgb0063
    Figure imgb0064
     und
    Figure imgb0065
EP04807680A 2003-12-26 2004-12-24 Ionische flüssigkeit, verfahren zu deren herstellung, doppelschichtiger kondensator, der diese enthält, und lithiumbatterie Not-in-force EP1698631B1 (de)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP2003431700 2003-12-26
JP2004019076 2004-01-27
JP2004019074 2004-01-27
JP2004094275 2004-03-29
JP2004094293 2004-03-29
JP2004285706 2004-09-30
PCT/JP2004/019323 WO2005063773A1 (ja) 2003-12-26 2004-12-24 イオン性液体、その製造法、それを含む二重層キャパシタおよびリチウム電池

Publications (3)

Publication Number Publication Date
EP1698631A1 EP1698631A1 (de) 2006-09-06
EP1698631A4 EP1698631A4 (de) 2009-03-11
EP1698631B1 true EP1698631B1 (de) 2011-08-10

Family

ID=34743976

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04807680A Not-in-force EP1698631B1 (de) 2003-12-26 2004-12-24 Ionische flüssigkeit, verfahren zu deren herstellung, doppelschichtiger kondensator, der diese enthält, und lithiumbatterie

Country Status (5)

Country Link
US (1) US20070099079A1 (de)
EP (1) EP1698631B1 (de)
JP (1) JP4310478B2 (de)
AT (1) ATE519767T1 (de)
WO (1) WO2005063773A1 (de)

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004017026A1 (de) * 2004-04-02 2005-10-20 Merck Patent Gmbh Ionische Flüssigkeiten mit Fluoralkyltrifluorborat-Anionen
JP4706067B2 (ja) 2004-12-27 2011-06-22 独立行政法人産業技術総合研究所 イオン液体
WO2006077894A1 (ja) * 2005-01-12 2006-07-27 Otsuka Chemical Co., Ltd. 第４級アンモニウム塩、電解質、電解液並びに電気化学デバイス
DE602006012933D1 (de) * 2005-01-12 2010-04-29 Otsuka Chemical Co Ltd Quaternäres ammoniumsalz, elektrolyt, elektrolytlösung und elektrochemisches gerät
KR101101001B1 (ko) 2005-01-19 2011-12-29 아리조나 보드 오브 리전트스, 아리조나주의 아리조나 주립대 대행법인 술폰계 전해질을 갖는 전류 생성 장치
JP2006236829A (ja) * 2005-02-25 2006-09-07 Nisshinbo Ind Inc イオン液体、蓄電デバイス用非水電解液および蓄電デバイス
US7737106B2 (en) * 2005-11-29 2010-06-15 The Procter & Gamble Company Process for making an ionic liquid comprising ion actives
GB0524700D0 (en) * 2005-12-03 2006-01-11 Bioniqs Ltd Liquids
DE102006005103A1 (de) * 2006-02-04 2007-08-09 Merck Patent Gmbh Oxonium- und Sulfoniumsalze
EP1819005A1 (de) * 2006-02-13 2007-08-15 Ecole Polytechnique Fédérale de Lausanne (EPFL) Ionische Flüssigkeit als Elektrolyt verwendbar
JP4997610B2 (ja) * 2006-12-28 2012-08-08 独立行政法人産業技術総合研究所 プラスティッククリスタル
JP5268007B2 (ja) * 2008-05-09 2013-08-21 独立行政法人産業技術総合研究所 イオン液体
JP5473296B2 (ja) * 2008-11-04 2014-04-16 大塚化学株式会社 第４級アンモニウム塩
EP2502295A1 (de) 2009-11-19 2012-09-26 Technion Research & Development Foundation Ltd. Silicium-luftbatterie
US8795544B2 (en) 2010-06-30 2014-08-05 Semiconductor Energy Laboratory Co., Ltd. Power storage device, lithium-ion secondary battery, electric double layer capacitor and lithium-ion capacitor
CN102532090B (zh) * 2010-12-29 2013-11-27 武汉艾奥立化学科技有限公司 含吗啉类离子型化合物作为合成环状碳酸酯的催化剂的用途
JP5778625B2 (ja) 2011-06-03 2015-09-16 株式会社半導体エネルギー研究所 イオン液体、及びイオン液体を含む蓄電装置
JP6099887B2 (ja) * 2011-06-24 2017-03-22 株式会社半導体エネルギー研究所 蓄電装置
CN102887850A (zh) * 2011-07-18 2013-01-23 海洋王照明科技股份有限公司 含吡咯烷离子液体、其制备方法和应用
JP6151910B2 (ja) 2011-12-23 2017-06-21 株式会社半導体エネルギー研究所 イオン液体、非水溶媒、電解液、蓄電装置
KR20130073822A (ko) 2011-12-23 2013-07-03 가부시키가이샤 한도오따이 에네루기 켄큐쇼 이온 액체, 비수 전해질 및 축전 장치
KR20140045880A (ko) 2012-10-09 2014-04-17 가부시키가이샤 한도오따이 에네루기 켄큐쇼 축전 장치
US20150140449A1 (en) 2013-11-15 2015-05-21 Semiconductor Energy Laboratory Co., Ltd. Compound, nonaqueous electrolyte, and power storage device
KR102305766B1 (ko) 2014-03-31 2021-09-27 가부시키가이샤 한도오따이 에네루기 켄큐쇼 전력 저장 장치 및 전자 장치
US10497979B2 (en) 2014-10-10 2019-12-03 Semiconductor Energy Laboratory Co., Ltd. Power storage device and electronic device
US10158108B2 (en) 2014-10-24 2018-12-18 Semiconductor Energy Laboratory Co., Ltd. Power storage device including separator surrounding electrode
US20160268064A1 (en) 2015-03-09 2016-09-15 Semiconductor Energy Laboratory Co., Ltd. Power storage device and electronic device
US10658701B2 (en) 2016-01-29 2020-05-19 Semiconductor Energy Laboratory Co., Ltd. Storage battery, battery control unit, and electronic device
JP2020094009A (ja) * 2018-12-14 2020-06-18 日清紡ホールディングス株式会社 サッカリンアニオンを有するアンモニウム塩
JP7474768B2 (ja) 2018-12-21 2024-04-25 ノームズ テクノロジーズ インコーポレイテッド ホウ素を含む変性イオン液体
TWI740690B (zh) 2020-10-23 2021-09-21 財團法人工業技術研究院 緩衝減震結構組合、車輛之緩衝減震結構以及車輛

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1205480A2 (de) * 2000-11-10 2002-05-15 MERCK PATENT GmbH Tetrakisfluoroalkylborat-Salze und deren Verwendung als Leitsalze

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1242483A (en) * 1983-10-26 1988-09-27 Toshikazu Shishikura Secondary battery
US6072692A (en) * 1998-10-08 2000-06-06 Asahi Glass Company, Ltd. Electric double layer capacitor having an electrode bonded to a current collector via a carbon type conductive adhesive layer
JP4817484B2 (ja) * 2000-09-26 2011-11-16 パナソニック株式会社 非水電解液およびそれを含む非水電気化学装置
CA2441981C (en) * 2001-03-26 2012-05-15 Nisshinbo Industries, Inc. Ionic liquids, electrolyte salts for electrical storage devices, liquid electrolytes for electrical storage devices, electrical double-layer capacitors, and secondary batteries
WO2002101773A1 (en) * 2001-05-11 2002-12-19 Mitsubishi Chemical Corporation Electrolytic solution for electrolytic capacitor and electrolytic capacitor using it
EP1365427B1 (de) * 2002-04-22 2008-03-19 Asahi Glass Co., Ltd. Elektrischer Doppelschichtkondensator
JP4322004B2 (ja) * 2002-11-22 2009-08-26 株式会社トクヤマ オニウム塩

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1205480A2 (de) * 2000-11-10 2002-05-15 MERCK PATENT GmbH Tetrakisfluoroalkylborat-Salze und deren Verwendung als Leitsalze

Also Published As

Publication number Publication date
JP4310478B2 (ja) 2009-08-12
WO2005063773A1 (ja) 2005-07-14
JPWO2005063773A1 (ja) 2007-12-20
ATE519767T1 (de) 2011-08-15
EP1698631A1 (de) 2006-09-06
US20070099079A1 (en) 2007-05-03
EP1698631A4 (de) 2009-03-11

Similar Documents

Publication Publication Date Title
EP1698631B1 (de) Ionische flüssigkeit, verfahren zu deren herstellung, doppelschichtiger kondensator, der diese enthält, und lithiumbatterie
US9006457B2 (en) Reactive ionic liquids
Forsyth et al. N-methyl-N-alkylpyrrolidinium tetrafluoroborate salts: ionic solvents and solid electrolytes
EP2090565B1 (de) Ionische Flüssigkeiten von quaternären Ammoniumsalzen
US8247117B2 (en) Ionic liquid
JP5339542B2 (ja) イオン液体
Belhocine et al. New ionic liquids from azepane and 3-methylpiperidine exhibiting wide electrochemical windows
JP4322004B2 (ja) オニウム塩
US20080204972A1 (en) Electric Double Layer Capacitor
EP1536440B1 (de) Elektrischer doppelschichtkondensator
Belhocine et al. Azepanium ionic liquids
EP1414088A1 (de) Neuartiges oniumsalz, elektrolyt für eine wasserfreie zelle mti dem neuartigen oniumsalz für eine wasserfreie zelle und verfahren zur optimierung einer negativ-elektrode unter verwendung eines oniumsalz enthaltenden elektrolyts
Zhou et al. A new class of hydrophobic ionic liquids: Trialkyl (2-methoxyethyl) ammonium perfluoroethyltrifluoroborate
US8345407B2 (en) Low viscosity ionic liquids
Min et al. Synthesis and physicochemical properties of ionic liquids: 1-alkenyl-2, 3-dimethylimidazolium tetrafluoroborates
KR101586356B1 (ko) 액정 특성을 가지는, 전해질로서 유용한 신규 이미다졸리움 염
EP2910558B1 (de) Ionische flüssigkeit
US9196424B2 (en) Double-center bipyridyl cationic ion liquid, preparation method therefor and use thereof
JP2005179254A (ja) 常温溶融塩およびその製造方法
CN106117217B (zh) 一种氟锆酸盐的制备方法
CN107021893A (zh) 一类硫代酰铵盐离子液体及其制备方法
JP2010111599A (ja) イオン液体およびその製造方法、並びにこのイオン液体を用いた蓄電装置
US8765296B2 (en) Ionic liquid
CN104505264B (zh) 一种无卤素螺环季铵盐的合成方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060703

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20090211

17Q First examination report despatched

Effective date: 20091208

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: C07F 5/02 20060101AFI20110121BHEP

Ipc: H01M 6/16 20060101ALI20110121BHEP

Ipc: H01G 9/038 20060101ALI20110121BHEP

Ipc: C07D 295/08 20060101ALI20110121BHEP

Ipc: C07D 295/02 20060101ALI20110121BHEP

Ipc: C07C 211/63 20060101ALI20110121BHEP

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RIN1 Information on inventor provided before grant (corrected)

Inventor name: MATSUMOTO, H.

Inventor name: ZHOU, Z.

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602004033923

Country of ref document: DE

Effective date: 20111117

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20110810

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20110810

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111210

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111212

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 519767

Country of ref document: AT

Kind code of ref document: T

Effective date: 20110810

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111111

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

26N No opposition filed

Effective date: 20120511

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111231

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20111224

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602004033923

Country of ref document: DE

Effective date: 20120511

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111224

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111231

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111231

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111110

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110810

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20141219

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151231

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20201020

Year of fee payment: 17

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602004033923

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220701